US4777023A - Preparation of silicon and germanium hydrides containing two different group 4A atoms - Google Patents
Preparation of silicon and germanium hydrides containing two different group 4A atoms Download PDFInfo
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- US4777023A US4777023A US06/830,103 US83010386A US4777023A US 4777023 A US4777023 A US 4777023A US 83010386 A US83010386 A US 83010386A US 4777023 A US4777023 A US 4777023A
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- 239000010703 silicon Substances 0.000 title claims abstract description 33
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title description 13
- MWRNXFLKMVJUFL-UHFFFAOYSA-N $l^{2}-germane Chemical class [GeH2] MWRNXFLKMVJUFL-UHFFFAOYSA-N 0.000 title description 11
- 238000000034 method Methods 0.000 claims abstract description 42
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 150000004678 hydrides Chemical class 0.000 claims abstract description 28
- 150000003839 salts Chemical class 0.000 claims abstract description 25
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 24
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 24
- 150000004820 halides Chemical class 0.000 claims abstract description 24
- 150000002678 macrocyclic compounds Chemical class 0.000 claims abstract description 24
- QUZPNFFHZPRKJD-UHFFFAOYSA-N germane Chemical compound [GeH4] QUZPNFFHZPRKJD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052986 germanium hydride Inorganic materials 0.000 claims abstract description 18
- 229910052990 silicon hydride Inorganic materials 0.000 claims abstract description 18
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 16
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 13
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 38
- 150000003983 crown ethers Chemical class 0.000 claims description 20
- 239000011591 potassium Substances 0.000 claims description 17
- 229910052700 potassium Inorganic materials 0.000 claims description 16
- 229910000077 silane Inorganic materials 0.000 claims description 15
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 14
- 239000007795 chemical reaction product Substances 0.000 claims description 14
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 13
- 229910000078 germane Inorganic materials 0.000 claims description 8
- -1 silicon halide Chemical class 0.000 claims description 7
- JIMODRYHNQDMSX-UHFFFAOYSA-N [GeH2].[Si] Chemical compound [GeH2].[Si] JIMODRYHNQDMSX-UHFFFAOYSA-N 0.000 claims description 5
- WQLQSBNFVQMAKD-UHFFFAOYSA-N methane;silicon Chemical compound C.[Si] WQLQSBNFVQMAKD-UHFFFAOYSA-N 0.000 claims description 5
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical group Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims description 2
- 239000005046 Chlorosilane Substances 0.000 claims 1
- 229910021417 amorphous silicon Inorganic materials 0.000 abstract description 16
- 230000008021 deposition Effects 0.000 abstract description 14
- 229910045601 alloy Inorganic materials 0.000 abstract description 13
- 239000000956 alloy Substances 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 11
- 230000015572 biosynthetic process Effects 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000004065 semiconductor Substances 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 54
- 229910052757 nitrogen Inorganic materials 0.000 description 27
- 229910003828 SiH3 Inorganic materials 0.000 description 22
- OLRJXMHANKMLTD-UHFFFAOYSA-N silyl Chemical compound [SiH3] OLRJXMHANKMLTD-UHFFFAOYSA-N 0.000 description 20
- 239000007788 liquid Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 9
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 5
- WHYHZFHCWGGCOP-UHFFFAOYSA-N germyl Chemical compound [GeH3] WHYHZFHCWGGCOP-UHFFFAOYSA-N 0.000 description 5
- 238000004949 mass spectrometry Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000011010 flushing procedure Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229920006384 Airco Polymers 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- XQQZRZQVBFHBHL-UHFFFAOYSA-N 12-crown-4 Chemical compound C1COCCOCCOCCO1 XQQZRZQVBFHBHL-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- VJFOQKOUHKDIGD-UHFFFAOYSA-N [GeH3][SiH3] Chemical compound [GeH3][SiH3] VJFOQKOUHKDIGD-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- AZFVLHQDIIJLJG-UHFFFAOYSA-N chloromethylsilane Chemical compound [SiH3]CCl AZFVLHQDIIJLJG-UHFFFAOYSA-N 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 description 1
- 150000003985 15-crown-5 derivatives Chemical group 0.000 description 1
- AUFVJZSDSXXFOI-UHFFFAOYSA-N 2.2.2-cryptand Chemical compound C1COCCOCCN2CCOCCOCCN1CCOCCOCC2 AUFVJZSDSXXFOI-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910000799 K alloy Inorganic materials 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 229910000528 Na alloy Inorganic materials 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005474 detonation Methods 0.000 description 1
- QSBFECWPKSRWNM-UHFFFAOYSA-N dibenzo-15-crown-5 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOC2=CC=CC=C21 QSBFECWPKSRWNM-UHFFFAOYSA-N 0.000 description 1
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 description 1
- UNTITLLXXOKDTB-UHFFFAOYSA-N dibenzo-24-crown-8 Chemical compound O1CCOCCOCCOC2=CC=CC=C2OCCOCCOCCOC2=CC=CC=C21 UNTITLLXXOKDTB-UHFFFAOYSA-N 0.000 description 1
- BBGKDYHZQOSNMU-UHFFFAOYSA-N dicyclohexano-18-crown-6 Chemical compound O1CCOCCOC2CCCCC2OCCOCCOC2CCCCC21 BBGKDYHZQOSNMU-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052730 francium Inorganic materials 0.000 description 1
- KLMCZVJOEAUDNE-UHFFFAOYSA-N francium atom Chemical compound [Fr] KLMCZVJOEAUDNE-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- UDNUMJGZDOKTFU-UHFFFAOYSA-N germanium;methane Chemical compound C.[Ge] UDNUMJGZDOKTFU-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- HVXTXDKAKJVHLF-UHFFFAOYSA-N silylmethylsilane Chemical compound [SiH3]C[SiH3] HVXTXDKAKJVHLF-UHFFFAOYSA-N 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
- C01B6/24—Hydrides containing at least two metals; Addition complexes thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
- C01B6/003—Hydrides containing only one metal and one or several non-metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0896—Compounds with a Si-H linkage
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
Definitions
- the present invention relates to a method for preparing hydrides containing at least two different atoms from Group 4A of the Periodic Table wherein at least one of the Group 4A atoms is silicon or germanium.
- Such hydrides can be used as deposition feedstock materials for the formation of hydrogenated amorphous silicon alloy films in the fabrication of photovoltaic devices and other semiconductor devices.
- alloys of magnesium and different Group 4A metals are reacted with acid.
- Other methods for preparing these materials include: pyrolysis of a germane with a silane; and the reaction of hydrofluoric acid on a mixed SiO-GeO preparation. See Timms et al.
- a further object of the present invention is to provide deposition feedstock materials for use in the formation of hydrogenated amorphous silicon alloys in the fabrication of photovoltaic devices or other semiconductor devices.
- Another object of the present invention is to provide novel coordinated salts of silicon and germanium hydride for use in preparing silicon and germanium hydrides containing two different Group 4A atoms.
- the invention comprises a method for preparing a hydride containing at least two different Group 4A atoms wherein at least one of the Group 4A atoms is silicon or germanium, comprising the steps of: (a) reacting an alkali metal and a macrocyclic compound with a silicon or germanium hydride to form a salt; and (b) reacting the salt formed in step (a) with a halide containing a different Group 4A atom.
- the invention also comprises a method for preparing a silicon germanium hydride comprising the steps of (a) reacting an alkali metal and a macrocyclic compound with a silicon or germanium hydride to form a salt; and (b) reacting the salt formed in step (a) with a silicon or germanium halide selected so that one of the hydride or halide contains silicon and the other contains germanium.
- the invention additionally comprises a method for preparing a silicon carbon hydride comprising the steps of (a) reacting an alkali metal and a macrocyclic compound with a silicon hydride to form a salt; and (b) reacting the salt formed in step (a) with an organic halide.
- the invention additionally comprises a coordinated salt of a Group 4A hydride comprising a cation and an anion wherein the cation is coordinated to a macrocyclic compound and the anion is a silicon hydride or a germanium hydride.
- FIG. 1 is an illustration of a photovoltaic device (not to scale) which can be fabricated using the silicon or germanium hydrides made in accordance with the process of the present invention.
- a method for preparing a hydride containing at least two different Group 4A atoms wherein at least one of the Group 4A atoms is silicon or germanium in accordance with the present invention comprises the steps of (a) reacting an alkali metal and a macrocyclic compound with a silicon or germanium hydride to form a salt; and (b) reacting the salt formed in step (a) with a halide containing a different Group 4A atom.
- the salt formed in step (a) is a coordinated salt of a Group 4A hydride comprising a cation and an anion wherein the cation is coordinated to the macrocyclic compound and the anion is a silicon or germanium hydride.
- Group 4A atom refers to atoms of the elements in Group 4A of the Periodic Table, i.e., carbon (C), silicon (Si), germanium (Ge), tin (Sn) and lead (Pb).
- alkali metal refers to the metals in Group 1A of the Periodic Table, i.e., lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) and francium (Fr).
- the preferred alkali metals used in accordance with the present invention are lithium (Li), potassium (K) and sodium (Na).
- macrocyclic compound refers to a compound having 10 or more atoms in a ring.
- macrocyclic compound is intended to include both monocyclic and polycyclic macrocyclic compounds.
- Macrocyclic compounds useful in the present invention include crown ethers, substituted crown ethers, cryptates and substituted cryptates. These materials are normally complex and have no encompassing general formulas.
- a representative but non-exhaustive list of examples of crown ethers useful in the practice of the present invention includes: 12-crown-4, 15-crown-5, and 18-crown-6.
- a representative but non-exhaustive list of examples of substituted crown ethers useful in the practice of the present invention includes: dibenzo-18-crown-6 ether, dibenzo-24-crown-8-ether, dicyclohexyl-18-crown-6-ether and dibenzo-15-crown-5-ether.
- a representative but non-exhausive list of examples of cryptates useful in the practice of the present invention includes: 2,2,2-cryptate, 2,2,1-cryptate and 2,1,1-cryptate.
- a representative but non-exhaustive list of examples of substituted cryptates useful in the practice of the present invention includes: alkyl-2,2,2-cryptate ether, benzo-2,2,2-cryptate.
- analogs of crown ethers containing silicon, nitrogen or sulfur and analogs of cryptates containing nitrogen or sulfur are also useful in the practice of the present invention as they also form macrocyclic strucutres with large interior holes similar to the holes formed in the center of the crown ethers, substituted crown ethers, cryptates and substituted cryptates.
- Representative examples of structures of such analogs are: ##STR1##
- the macrocyclic compound used should be selected to complement the alkali metal which is being used. That is, the shape of the hole in the center of the macrocyclic compound should complement the size of the alkali metal.
- 12-crown-4 is the preferred crown ether to use with lithium (Li) as the alkali metal.
- the preferred crown ether is 15-crown-5.
- 18-crown-6 is the preferred crown ether to use with the alkali metal potassium (K). Good results have been obtained using potassium as the alkali metal and 18-crown-6 as the macrocyclic compound to which it is coordinated.
- the hydride used in step (a) is either a silicon hydride or a germanium hydride. Selection of one or the other will depend on the final product desired.
- silicon hydride refers to compounds of the formula:
- M is one or more Group 4A atoms.
- the sum of A and B is an integer between 1 and 5, inclusive.
- a representative but not exhaustive list of examples of silicon hydrides useful in the practice of the present invention includes: SiH 4 , SiCH 6 , SiGeH 6 , Si 2 CH 8 , Si 2 GeH 8 , Si 3 GeH 10 and Si 3 CH 10 .
- the preferred silicon hydride to use in practicing the present invention is silane (SiH 4 ).
- germanium hydride refers to compounds of the formula:
- M is one or more Group 4A atoms.
- the sum of A and B is an integer between 1 and 5 inclusive.
- a representative but not exhaustive list of preferred examples of germanium hydrides useful in the practice of the present invention includes: GeH 4 , GeCH 6 , GeSiH 6 , Ge 2 CH 8 Ge 2 SiH 8 , Ge 3 SiH 10 , and Ge 3 SiH 10 .
- the preferred germanium hydride to use in practicing the present invention is germane (GeH 4 ).
- the halide containing a different Group 4A atom used in step (b) of the process of the present invention should also be selected on the basis of the desired end product.
- the end product desired is a silicon germanium hydride
- at least one of the halide and hydride should contain a silicon atom and at least one of the halide and hydride should contain a germanium atom.
- the desired end product is a silicon carbon hydride
- a silicon hydride should be used with an organic halide.
- a germanium carbon hydride is desired, then a germanium hydride should be used with an organic halide.
- halides containing a different Group 4A atom can be used in practicing step (b) of the present invention. Good results have been obtained using CH 3 I, CH 2 Cl 2 , or SiH 3 Cl as the halide containing a different Group 4A atom.
- step (a), i.e., the salt formation step occurs at room temperature i.e, 20°-25° C.
- the pressure is preferably atmospheric pressure or above.
- an ether containing solvent is used.
- Preferred ether containing solvents include monoglyme (CH 3 OCH 2 CH 2 OCH 3 ) and diglyme (CH 3 OCH 2 CH 2 OCH 2 CH 2 OCH 3 ).
- Reaction time will vary depending on the hydride used. Agitation of the reaction mixture is preferred. Typical reaction times range from 30 minutes to 24 hours with suitable agitation.
- step (b) i.e., the reaction with a halide step is exothermic. Consequently, it is preferable to cool the reactants and then let the reaction mixture warm to room temperature.
- the reactants are cooled to a temperature of between -100° C. and 0° C. The best temperature within this range will vary depending on the particular solvents and reactants used.
- the reaction is largely independent of pressure and thus any suitable pressure can be used. Atmospheric pressure or below is preferred since too high a pressure may slow down the voltization of the product.
- Reaction time is dependent on how fast the reaction mixture is warmed to room temperature. Preferably, this is done in less than 30 minutes.
- a 500 ml gas bulb was evacuated and filled with nitrogen. 3 ml of tin tetrachloride (SnCl 4 ) (Alfa Products®) and 0.56 gms of silane (SiH 4 ) (Airco®) were added to the bulb. The bulb was sealed off and allowed to sit overnight (15-19 hours) at room temperature. The product was distilled and silylchloride (SiH 3 Cl) was collected.
- SnCl 4 tin tetrachloride
- SiH 4 SiH 4
- Airco® silane
- a 250 cc flask was degassed 0.195 gm of potassium (K) (Alfa Products®) and 1.58 gm of 18-crown-6 (Aldrich®) were added to the flask while flushing the flask with nitrogen.
- K potassium
- 18-crown-6 18-crown-6
- Four ml of distilled monoglyme (CH 3 OCH 2 CH 2 OCH 3 ) (Aldrich®) was added to the flask while continuing to flush with nitrogen.
- the flask was then sealed and frozen in liquid nitrogen. Nitrogen was then evacuated from the flask and 0.38 gm of germane (GeH 4 ) (Matheson®) was added to the flask. After sealing, the flask was warmed to room temperature while stirring the reaction mixture for 30 minutes to obtain [K 18-crown-6] + GeH 3 - .
- a 250 cc flask was degassed. 0.225 gm of potassium (K) (Alfa Products®) and 1.94 gm of 18-crown-6 (Aldrich®) were added to the flask while flushing the flask with nitrogen. Six ml of distilled monoglyme (Aldrich®) was added to the flask while continuing to flush with nitrogen. The flask was sealed and frozen in liquid nitrogen. The nitrogen was evacuated from the flask and 0.16 gm of silane (SiH 4 ) (Airco®) was added to the flask. After sealing with a stopcock, the flask was warmed to room temperature while stirring the reaction mixture for 3 hours to obtain [K 18-crown-6] + SiH 3 - .
- SiH 4 silane
- a 250 cc flask was degassed. 0.235 gm of potassium (K) (Alfa Products®) and 2.0 gm of 18-crown-6 (Aldrich®) were added to the flask while flushing the flask with nitrogen. Eight ml of distilled monoglyme (Aldrich®) was added to the flask while continuing to flush with nitrogen. The flask was sealed and then frozen in liquid nitrogen. The nitrogen was evacuated from the flask and then 0.25 gm of SiH 4 (Airco®) was added to the flask. After sealing, the flask was warmed to room temperature while stirring the reaction mixture overnight (approximately 15-18 hours) to obtain [K 18-crown-6] + SiH 3 - .
- K potassium
- Aldrich® 18-crown-6
- Solvent was drawn from the flask with a vacuum pump and the flask was frozen in liquid nitrogen. 0.2 gm of methylene chloride (CH 2 Cl 2 ) (Aldrich) was added to the flask and the flask was sealed. Over 15 minutes the flask was allowed to warm to room temperature. Product was collected in a liquid nitrogen trap. The sample was analyzed by GC/mass spec and a yield of 19% SiH 3 CH 2 SiH 3 was obtained. Other by-products also present in the reaction product were silane, methylsilane and chloromethylsilane.
- CH 2 Cl 2 methylene chloride
- a 250cc flask was degassed. 0.235 gm of potassium (K) (Alfa Products®) and 2.0 gm of 18-crown-6 (Aldrich®) were added to the flask while flushing the flask with nitrogen. 100 ml of distilled monoglyme (Aldrich®) was added to the flask while continuing to flush with nitrogen. The flask was sealed and frozen in liquid nitrogen. The nitrogen was evacuated from the flask and 0.25 gm of SiH 4 was added to the flask. After sealing, the flask was warmed to room temperature while stirring the reaction mixture overnight (15-18 hours) to obtain [K 18-crown-6] + SiH3 - .
- Solvent was drawn from the flask with a vacuum pump and the flask was frozen in liquid nitrogen. 0.2 gm of CH 2 Cl 2 (Aldrich®) was added to the flask and the flask was sealed. Over 15 minutes the flask was allowed to warm to room temperature. Poduct was collected in a liquid nitrogen trap. The sample was analyzed by GC/mass spec and a yield of 36% SiH 3 CH 2 SiH 3 was obtained. Other by-products present in the reaction product were silane, methylsilane, disilane, and chloromethylsilane.
- the Group 4A hydrides made in accordance with the process of the present invention are useful as deposition feedstock materials in the formation of hydrogenated amorphous silicon alloys used in the fabrication of photovoltaic devices. This is discussed in greater detail in copending U.S. patent application Ser. No. 06/830,073 of Charles Robert Dickson, entitled “Deposition Feedstock Materials Useful in the Fabrication of Amorphous Silicon Alloys for Photovoltaic Devices," filed concurrently herewith, the disclosure of which is incorporated herein by reference.
- atoms from Group 4A of the Periodic Table such as carbon and germanium
- hydrogenated amorphous silicon alloys in order to adjust their optical bandgap.
- carbon has a larger bandgap than silicon and thus inclusion of carbon in a hydrogenated amorphous silicon alloy increases the alloy's bandgap.
- germanium has a smaller bandgap than silicon and thus inclusion of germanium in such an alloy decreases the alloy's bandgap.
- Hydrogenated amorphous silicon alloy films are conventionally prepared by glow discharge deposition in a deposition chamber.
- a silicon or germanium hydride made in accordance with the present invention as a deposition feedstock material included in the deposition gas mixture introduced into the deposition chamber, the incorporation of desired Group 4A atoms into the hydrogenated amorphous silicon alloy can be better controlled and undesirable dangling electron bonds can be reduced or eliminated.
- FIG. 1 is an illustration of a photovoltaic device which can be fabricated using the silicon or germanium hydrides made in accordance with the process of the present invention.
- light (1) enters the light incident side of the photovoltaic cell.
- the light passes first through a glass layer (2), then through a transparent conductive layer (3) and then into a multilayered hydrogenated amorphous silicon region (4).
- a metal back contact (5) is also on the side opposite the light incident side of the photovoltaic device.
- the multilayered amorphous silicon region (4) is a p-i-n junction. That is, the multilayered amorphous silicon region includes a positively doped layer (p-layer) (6), an intrinsic layer i-layer) (7) and a negatively doped layer (n-layer) (8).
- p-layer a positively doped layer
- n-layer a negatively doped layer
- a conventional hydrogenated amorphous silicon photovoltaic cell having a p-i-n junction of this same general form is shown, for example, in U.S. Pat. No. 4,217,148, the disclosure of which is incorporated by reference herein.
- a silicon germanium hydride is prepared by the steps of (a) reacting an alkali metal and a macrocyclic compound with a silicon or germanium hydride to form a salt; and (b) reacting the salt formed in step (a) with a silicon or germanium halide selected so that one of the hydride or halide contains silicon and the other contains germanium.
- Silicon germanium hydrides prepared by this method are particularly suitable as deposition feedstock materials for forming i-layers or n-layers in p-i-n type photovoltaic devices such as is illustrated in FIG. 1.
- a silicon carbon hydride is prepared by the steps of (a) reacting an alkali metal and a macrocyclic compound with a silicon hydride to form a salt and (b) reacting the salt formed in step (a) with an organic halide.
- Silicon carbon hydrides prepared by this method are particularly suitable as deposition feedstock material for forming p-layers in p-i-n type photovoltaic devices such as illustrated in FIG. 1.
- Examples 6 and 7 illustrate uses of the silicon and germanium hydrides made by the process of the present invention in the formation of hydrogenated amorphous silicon alloy layers in the fabrication of p-i-n junctions such as is illustrated in FIG. 1.
- a 100 ⁇ thick amorphous silicon carbon p-layer is formed using a deposition gas mixture containing 15 SCCM of disilylmethane, (SiH 3 ) 2 CH 2 , prepared by the method described in example 5, 12 SCCM of 11/2% diborane, B 2 H 6 , in silane, SiH 4 , and 73 SCCM of silane.
- the p-layer is deposited in a D.C. glow discharge using a cathode current density of 0.14 ma/cm 2 , a substrate temperature of 220° C. and a total gas pressure of 0.5 torr.
- a 2500 ⁇ thick amorphous silicon germanium i-layer is formed using a deposition gas mixture containing 5 SCCM of monosilylgermane, SiH 3 GeH 3 , prepared by the method described in example 2, and 95 SCCM of silane, SiH 4 .
- the i-layer is deposited in a D.C. glow discharge using a cathode current density of 0.09 ma/cm 2 , a substrate temperature of 220° C. and a total gas pressure of 0.5 torr.
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Abstract
Description
Si.sub.A M.sub.B H.sub.(2(A+B)+2)
Ge.sub.A M.sub.B H.sub.(2(A+B)+2)
Claims (15)
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US06/830,103 US4777023A (en) | 1986-02-18 | 1986-02-18 | Preparation of silicon and germanium hydrides containing two different group 4A atoms |
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